Process for breaking petroleum emulsions



fiateniecl May 2 1956 'umr enoonssEGKTBRE KiNG ETRGLEUM EMULSIONS Melvin D'e Gi-oote,Universitf'Gity, and Bernhai-uf 'Kei'ser, 'Vihebster -Groves, -'Mo., assignors to Petrolite "Corporation, Ltd., -Wilmington, =Del.,- a corporation of Delaware "Nb Drawing. "'A'pplicationMarch '12, 1947, Serial No. 7 345206 6 Claims. (01. 2524342) This invention relates tomew chemical products I or compounds and to the use and manufacture of same.

One object of our invention is to provide new chemical products or compounds that are particularly adapted for 'useras a demulsifier in petroleum emulsions, and which are also capable of various other uses as hereinafter described.

Another object ofour invention is to provide a practical method ofmaking the said compounds or chemical products.

Another object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil'type that are commonly referred to as cut oil, emiilsified oil, roily oil, 1

Demulsification as contemplated in the present (application, includes theipreventive step of com gmingling the demulsifier withthe aqueous compo- :nent which wouldbr'mieht subsequently become .sifier may be mixed wlthdhe-hydrocarbon component.

' Briefly stated, the new chemical compounds Therein contemplated and particularly for use as fdeiniilsifying agents, are obtained bythe reaction bf'certa'm polyethylene"glycols'with certain acidic fractional esters of' triifcinole'in. "Suchacfdic estersare obtained by 'reactingtriricinoleinwith :one to three molesof polycarboxyacld and'pariticlllarly a dicarboiry acid such" as phthalic"aci d, :adipic acid, diglycolic acid,etc.,with the proviso :that such acid'be free rrom'al hametaunsatp- .ration, thus eliminating dicarboxy acids having activedinophylic components or structuressuch as maleic anhycliidaeitraconic a'nhydfide; etc

, The hereto appended "claims are liniited to derivatives'of dicarboxy acid or anli'ydrides.

--Acidic esters of tririclnolein; can bemanufactured in two different ways, although using'the amageneral procedure. bne' method and use temperatures not in excess of-i2l0 and inabsence of' any acatalys't. Under such circumstances one forms the expe cted esters in" which thedicarbon-y acid radical is invariably attached to the ricinrol'eylshydroxyl. The vsecond procedureinvolves the :use fof temperatures" higher than- 210 the presence or absencefof catalysts ase-that a certain samount of rearrangement may =take;plac e, :with the result sthat -the I dicarboxyacid radical maybeattached to the---glyceryl radical 1 andcnot limitedfiito attachment to ther icino-leyl radical; Thisilaitervtypeaof structure will -be clari-fled'=by subsequent :description. It 'isto "benoted; however, that the compoundsmontemplatedherein are xthose obtained'rfromintermediates .in which the dicarboxy'aacidwradical is attached-to ethe ricinoleylr radical and thus excludes acidic aStr obtained by; rearrangement at higher stempera tures or in presence of catalysts.

The manufacture of fractional esters of triricinoleinis well known and described in numerous patents. "The literature, including' various patents, also' de'sc'ribe's' the esterification'cofi:subh fractional esters with polyhy'd ric alcoh'olspinclud 'ing' o1y 1y'co1s under ilarious conditions invblve ing, for exampleg' eitlrer the presence oraabsen'ce of catalysts or a variety -of catalysts, including both acid and basic -catalysts. 7

Attention is directed to our co -pending application, Serial lIofibGEiilQfifild May 2, 1946, now

abandoned. :"Said eopendina application is concerned with tlie lioxyalkylation, rz particularlyetl e oxyethylation, of thesammacidic fractional esters as herein employed for reaction with nonaethyleneglycol or the like. In' our said aforementioned co-pending application, "Seria1 No. 666,819, we 'Statedras follows: It=has=been-.suggested that the reaction ofra fractionalester"witha polyethylene glycol under various .cen'd-itions would; in essence, result :in a product substantially-the samelas that obtained by reacting with ethylene oxide so as to obtain the same stoichiometric relationship. "We have found that this .is notthexcase and that'the resultant productsare significantly different in composition, and those products obtained by oxyethylation are much moryeffective for a number of. purposes, such as, for example, demulsification of ii petroleum emulsions, break inducer in doctor treatment of sour hydrocarbons, etc. Alth'oiiglr'wehave found the products obtained by oxyalkylation of-these particular esters to be particularly desirable and in many cases superior to those obtained by reaction with nonaethylene- .gl ycol or the like,yet in a number of instances the resultant obtained from the reaction involvvolves the inherent nature of the reactants andv resultants, and it is deemed desirable to point out clearly the nature of the product obtained when triricinolein is reacted with polycarboxy acids, and particularly those having 4 to 8 carbon atoms, and particularly dicarboxy acids having 4 to 8 carbon atoms, such as succinic acid, adipic acid, diglycolic acid, and phthalic acid, subject to the previous limitation excluding maleic anhydride, etc. The anhydrides, of course, are the obvious equivalent of the acid and include, among others, phthalic anhydride, etc. Other suitable acids, include oxalic, tricarballylic, tartaric, azelaic, sebacic, etc. Other acids include cis-A -tetrahydrophthalic anhydride obtained by the action of butadiene on mal'eic anhydride, and 3,6-endomethylene-A tetrahydrophthalic anhydride obtained by the action of cyclopentadiene on maleic anhydride. It is to be noted that none of these acids have more than 10 carbon atoms. As stated, it is understood that the acids and anhydrides are con sidered as equivalents.

A preferred ester product may be obtained by esterification reaction between triricinolein and a dibasic carboxylic acid such as phthalic acid. Ricinoleic acid may be indicated by the following formula:

and contains the residue of the polyhydric alcohol glycerol which maybe represented as HOCH:

HO H B04313:

Triricinolein readil esterifies with phthalic acid and if three moles of phthalic anhydride or acid are caused to react with one mole of triricinolein, a fractional acidic ester will be obtained according to the following reaction:

HORCOQCH: o +HoRoood1-1 HORCOOJJH @oooncoocm COOH' COOROOO H 7 COOH COOROOO H:

It is not necessary to use three moles of phthalic anhydride per mole of triricinolein and if desired, one may use one or two moles although the preference is to use approximately 2 to 2 /2 or 3 moles. Likewise, in carrying on the sterification reactions broadly, without limitation to the particular type herein employed as intermediates, it is not essential that a carboxylic group of the dibasic carboxylic acid react with the alcoholiform hydroxyl in the ricinoleyl radical while the ricinoleyl radical remains directly connected with the polyhydric alcohol radical. One might react ricinoleic acid monophthalate, obtained by reaction between ricinoleic acid and phthalic anhydride, mole for mole, with glycerol in the ratio of three moles of the fractional ester for one mole of glycerol. This would yield a mixture of compounds such as the following:

HOOCROO COOCH:

HOOCROO (500011 HOOCROOO 4700 E:

HOOCROOC OOCH:

HOOCROOAJ 000 H H0O!) (500E000 Hz HOOCROO 00011, HOO( J gooaooo H HOOC ADOORCOO H:

Not only may compounds of the above type be obtained by the procedure previously described, but such compounds may occur to a greater or lesser degree as the result of molecular rearrangement in the production of acidic fractional esters from triricinolein and various polycarboxy acids as previously mentioned, provided one employs temperatures in excess of 210 C. or employs catalysts or both.

In carrying on the esterification reaction, there may develop cross-linkages either through the polyhydric alcohol or the polybasic carboxylic acid due to the polyfunctionality of these materials. For example, in an esterification reaction between triricinolein and phthalic acid, the resulting product may comprise more complex molecules such as the following which illustrate cross-linkage through the =polyhy'dric alcohol duce amixture of acid phthalates consistingfied r id sentia'lly of triricinolein dibasic ;phthalat'e :an'd triricinolein tribasic phthalate. The "reaction maybe caused to occur by heating the rnixefi 5 materials at-a temperaturerof approximately 120 moooonooo 00011 to 140 C. for approximatelyG-to 12 hours. The reaction can be followed roughly by withdrawing a small sampleof the partially reacted'mass-antl permitting it to'cool on avwatchcrystal. When 7 -13 ooonooo :003 thereaction has become completed, no crystals of phthalic anhydride appear. When the-sample no longer shows'the presence of such crystals on' (E cooling, it can be titrated withastandard vol- -11, 00012000 0011000011, umetric alkaline solution, since the acid :which 15 remains is due entirely to carboxylichydrogen in 1 4 O H OOOROO 00011 the fractional ester and not to any unreacted phthalic anhydride. If care is-takenmot to use "11135000110093 (BOO-R000 HI too high temperatures which would 'cause'formation ofheterocyclic bodies of thecharacter a'bove 2 referred-to, zone can depend upon the standard alkaline solution-to indicate the disappearance of H "000E000 OORGOOH the phthalic-anhydride. Itis not'to 'be inferred, however, that any-cyclic'bodies/if forme'd, 'would be-unsuitable.

1 The product thus obtainedyhowever, seems ito H, 0003000 001100011 consist largely of triricinolein dibasic phthalate 'Cross linkagelikewise may occur through the and triricinoleintribasicphthalate. Apparently polybasic carboxy'acidto afford molecular structhere is no evidence :of rearrangement. Ihisfa-et t gs h as is indicated by a molecular weight determina- 39 tion and'alsobased on the acid value which usually runs from a" little over 100 to =slight1y' iess 6 than 110. o

HO 0 O R 6 0 E TRIRICINOLEIN ACIDIC FRACTIQNALESM ER .HORCOO l H Ezmmpletz v I COORCOOOm -Sebacic acid is substituted for phthalic anhydride in preceding Example '1, to give the cor-'- COORCOOZH responding sebacic acid derivative,that is, tri- 110E000 H ricinolein dibasic sebacate andtriricinolein tri- H000 00012000611, 40 basic Sebacate- TRIRICINOLEIN ACIDICFRACTIONALESTEB Example 3 "It is apparent that other cross-linkages may Adipic acid or anhydric -is substituted for occur. Such ester products containing more 545 phthalic anhydrideinprecedingEx-ampleto complex molecules are also suitable. It is also give the correspondingadipic acid derivative,-tha t "apparent that 'theremay be "great-variations in is, 'triricinolein 'dibasic' a'dipate and triricinolein "the molecular weight of theproduct. The motribasic adipate.

lecular Weight'of the ester product as determined by cryoscopic methods 'or from obvious composi- 'TRIRICINOLEIN ACIDIC FRACTIQNAL'ESTEB tion of the ester, usually runs between about 300 'EwampZeA and about 4000 and is "seldom over-SOOO. Ester 'succinic acid or anhydride is substitutediot Pr duc S amolecular weight Over about phthal-ic anhydridein preceding -exampie, to-give 21 pr f r ly are p y du the the corresponding succinic acid derivative, --that 'esterification reaction there may besome D Y- is, triricinoleindibasic succinate and triricinolein =merization andpolymerized products as'well as t ib i i fi 'simple monomers may be used. 4 Attention isdirected to'what has been said pre- TRIRICINOLEIN ID C :FRA IQ AL viously for sakeofclarification andthat is, that ESTER the intermediates herein contemplated, that is 50 --the acidic esters derived by reaction between tri- Example 5 ricinolein and various dicarboxyacids or anhy- :Diglycolic acid is :substituted ;for phthalic drides,are limitedto those obtained by manu- :anhydride in :preceding Example ,1, to .;give 213116 facture under conditions whichpreclude drastic corresponding ,diglycolicacid derivative, that is, --rearrangements :and-thus are characterized by Jtriricino1ein dibasic diglycolate and triricinolein "the ifact that the dicarboxy acidradical is attribasic diglycolate. tached directly:to-thericinoleyl radical, and not The products of.esterificationproduced-accordto the glycerylradical. i-ng .to Examples .1 to 5 are viscous, yellowish or v T T amber .colored, oily :or sub-resinous .-materia1s, 'TRIRICINOLEIN ACIDC FRACTIOL'AL ESTER :resemblingsomewhat blown castor-oil in con- Emmple 1 :sistency,;and being water insoluble. 'One'pound mole of triricinolein (in the form of .It is to be noted that the 'tI'iIiCiHOlGiHlfiOidiO "castor oil which ordinarily contains approximate- :.fractional .esters'herein contemplated asthepre- .1 7 857% to :triricinolein) is reacted with :ferredureactants, are characterized by the [fact pound ..m0les .of-phthalic'anhydridewo pro- 1 that they are preferahlylobtained:byyesteriflcm awasse tionreactions involving the use of more than one mole of the polycarboxy acid per mole of triricinoleiri. For instance, previous formulas indicate combinations wherein 1 moles to 3 moles of phthalic anhydride are used per mole of triricinolein. In all instances, regardless of the ratio of polycarboxy reactant to triricinolein, there must be at least one free carboxyl per mole of triricinolein in the finished product. Such requirement is met, of course, by triricinolein monobasic phthalate derived from one mole of triricinolein and one mole of phthalic anhydride. Attention is also directed to the fact that all the fractional esters are prepared in such a manner that the final product is anhydrous. The next step is the obvious one of subjecting such anhydrous ester to the action of the polyglycol as herein specified.

,. The polyglycols which we employ, contain approximately 8 to 12 oxyethylenegroups. Our preference to use the oxyethylated compounds is due largely to the fact that they are commercially available, and particularly so in two desirable forms. The most desirable form is the so-called nonaethylene glycol, which, although consisting largely of nonaethylene glycol, may contain small amounts of heptaethylene and octaethylene gly- .cols, and possibly minor percentages of the higher homologs. Such glycols represent the upper range of distillable glycols; and they may be conveniently referred to as upper distillable ethylene glycols. There is no particularly good procedure for making a sharper separation on a commercial scale; and it is understood that mixtures of one or more of the glycols may be employed, as well as a single glycol. As pointed out,

it is particularly preferred to employ nonaethylene glycol as commercially available, although it is understood that this product contains other homologs, as indicated.

Substantially as desirable as the upper distillate polyethylene glycols, are the lower nondistillable polyethylene glycols. These materials are available in the form of a waxy water-soluble material, and the general range may vary somewhat from decato tetradecaethylene glycol. As

is well understood, the method of producing such glycols would cause some higher homologs to be formed; and thus, even in this instance, there may be present some oxyethylene glycols within the higher range above indicated. One need not point out that these particular compounds consist of mixtures, and that in some instances, particularly desirable esters are obtained by making mixtures of the liquid nonaethylene glycol with the soft, waxy, lower non-distillable polyethylene glycols. For the sake of convenience, reference in the examples will be to nonaethylene glycol; and calculations will be based on a theoretical molecular weight of 414. Actually, in manufacture, the molecular weight of the glycol employed, whether a higher distillable polyethylene glycol or a lower non-distillable polyethylene glycol, or a mixture of the same, should be determined, and reaction conducted on the basis of such determination, particularly in conjunction with the hydroxyl or acetyl value.

As previously pointed out, mere casual examination might lead one to believe that the resultant obtained by reacting acidic fractional esters,

such as triricinolein monophthalate, triricinolein the same as reacting with a corresponding amount of ethylene oxide.

, at a mid-point.

' If one examines the formula for ricinoleie acid, it becomes obvious that the polycarboxy acid, such as phthalic acid, becomes attached approximately half way in the carbon atom chain and thus oxyethylation, attacking any residual carboxy group which is part of the polycarboxy acid radical, must of necessity cause the hydrophile polyglycol group to enter or make its effectiveness felt half way in the carbon atom chain as difierentiated with the introduction of a hydrophile group at the end of a carbon atom chain. For instance, when a high molal alcohol or a high molal acid is subjected to oxyethylation, obviously such efiect is produced terminally and not In this connection, it is interesting to note that oxyethylation does not, as was one time believed, attack the secondary alcoholic radical of triricinolein when castor oilis subjected to oxyethylation. For this reason, oxyethylation of the fractional esters give a product having a hydrophobe-hydrophile balance which is entirely difierent from that obtained from a number of apparently kindred products.

Compounds herein contemplated, are obtained by esterifying free carboxyls with a glycol of the kind described. It is understood, however, that this particular specification does not include those types wherein such glycols would be re placed by polyhydric alcohols having a larger number of hydroxyl groups per molecule, i. e., does not include glycerol, diglycerol, trigiycerol, etc. Furthermore, the compounds herein contemplated, are derivedsolely from triricinolein and do not include compounds derived from monoricinolein, diricinolein, or any other type of fractional ester where the number of ricinoleic acid radicals is less than the valency of the polyhydric alcohol (the glyceryl radical) to which they are attached, valency of the radical in such circumstances being measured by the number of available hydroxyl groups, that is, the valency of a glyceryl radical being considered as 3. The reason for this difference is perfectly obvious, in that an available glyceryl hydroxyl radical, as in the case of a derivative of monoricinolein or diricinolein, provides an additional point of reaction for a polybasic acid, such as phthalic anhydride, or if not so reacted upon provides a point of reactionfor ethylene oxide. Similarly, if the acidic esters are esterified with glycid or methylglycid instead of ethylene oxide or the like, or glycerol for that matter, then such esters are capable of attack by ethylene oxide so as to provide a branched chain rather than a single chain involving polyglycol radicals. What has been said herein immediately preceding is intended to define the herein contemplated com; pounds with greater clarity and also to point out the line of demarcation between these particular compounds and those contemplated in our copending application, Serial No. 734,207, filed March 12, 1947.

Products of value as demulsifying agents, have been prepared by reacting triricinolein phthalates of the kind described under the heading Triricinolein acidic fractional esters, with polyhydric alcohols, although not necessarily with polyethylene glycols havinga large number of repetitious ether linkages, in such proportion and manner as to render such fractional esters water soluble or water miscible. At first casual examination, it would appear that if one were to react the acid phthalates as exemplified by Triricinolein acidic fractional ester, Example 75 1, with polyethylene glycol representing a p:-

proximately 10.0r 12, ethylene oxide-units. there.

should be obtained a product approximately identicalwith the. product obtained, by treatin triricinolein triphthalate, with approximately 30 to. 35 moles of ethylene. oxide. For instancathis. reaction may be indicated in. the. following manner:

' coonoooonr COORC0.0CHI,

+1: ans- C'OORCOOCHz' C 0 winionn involving ethylene oxide onthe one hand and a polyethyleneglycol on the, other, is this par ticular situation; The esters employed are polyfunctional, having, forexample preferably two or more carboxyls per original molecule of trir'icinolein The polyethylene glycols are difunetional; thus, when reacted together there is a; tendency to form a sub-resinous polyester by reactions involving simultaneously, one; mole of polyethylene glycol and two carboxylswhich are part of the same molecules, or-muchmore'probable, parts of two different molecules. The last mentioned reaction may be indicated by the following manner;

OOOH

nloocnooo' oonmoo-oono a I g moooonoo-o 0012000 11;-

H fooo'noo oon'ooon mooo'ono or) :0 one com wherein X is HOCHz-X-CHzOH representing the original polyethylene -g lyco1.

In light of whatiisvsaidrhereinafter; it; is, ob. vious' that the above {reactionrepresents? only; the firststep .or-partohthe, reactions 1 which yield the ultimate product.hereincontemplated. Theabove reaction shows esterification only and not pyrolysis. The reason is-, obvious by reference to the claims where it is specified that the amount of water evolved during pyrolytic esterification is at least twice that theoretically obtainable from the complete reaction ofthe free carboxyl radicals present.

In conneotion with whatvissaid herein in regard to the difference between oxyethylation on 40 the one handand esterification on the other hand, it must be remembered that oxyethylation takes place readily, and, rapidly at temperatures considerably under 200 C: and that this particular temperature may be considered the upper limit. Esterification as shown subsequently, invariably involves much higher temperatures, such as- 230 C. to 340 C.

In considering. what is. said herein as to the difierence in structure, it may be particularly DO convenient to refer toa single oxyethylated product derived from Triricinolein acidic fractional ester, Example 1. For. convenience We are going to describe this particular compound which is agsuitable basis :for comparison, in the samemai nen as:- ili-iSgdBSCIibBd 11110111. ooepending applicaai tion SBIiaILNQ': 6fi6,819'fi1ed;M y. 2-; 9

WATER 'S'OLUBLE OXYETHYLATE-D T-Rlf RICINOLEIN' FRACTIONAL ESTER 650 pounds of triricinolein acidic fractional ester manufactured as described under the headingExample-l-preceding, is mixed with pound of. sodium= methylateaand: then: reacted with approximately 161 pounds of ethylene oxide in three batches, of; .5317. po nds each. .The maximum pressure during the reaction was pounds per squareinch gauge presenter Thetime of reaction requiredforeaobbatchwas three to five hours. The vtemperature employed. was approximately C. The material was tested for watersolubility after: the-,addition, or 161 pounds of ethylene oxide and. found to be water insoluble. jeoretical'molcular,weight of triricinolein Y -tribasicl phthalate is -considered as 1360, then ithe average molecularwelght of the raw material employed was taken as 1300. On this basis, the amount of ethylene oxide added at this point, represented a molal ratio of 1 to 7.3 approximately.

Oxyethylation was then continued by the addition of three more portions of approximately 60 pounds each, so that at the end of the sixth batch, the molecular ratio had more than doubled and was approximately 1 to 18.0. The product at this point began to show some distinctly hydrophile character and solubility, but was'reacted further with five additional portions of approximately 65 pounds each. Thus the total amount of ethylene oxide added, represented 161 pounds, plus 180 pounds, plus 235 pounds, being a total of 666 pounds, of ethylene oxide added to 650 pounds of the original resin. On a weight-by-weight basis, this represented slightly in excess of 1 to 1, and on a molal basis, itrepresented approximately 30 to 32 moles of ethylene oxide per mole of monomeric fractional ester. The resultant was a thin, deep amber colored, water soluble product having a clear appearance in solution and good foaming proper ties. "W"

The product so obtained consists principally of oxyethylated triricinolein 'dibasic phthalate and oxyethylated triricinolein tribasic phthalate. The composition of these two compounds may be shown in the following manner:

-oo ounonn COORCOOTHz v H(OH4C2),.OOC COOROOOCH -COORCOO(LH5 OOO(C2H40)'|H -ooo o,H4o)..H

ooonooooro HORCOO H -o0o1toooom -ooo oimo)..n

In the above formulae, the value of n varies on the average from to 11 in the case of the tribasic derivative and from 12 or 13 for the dibasic product. The acid value of this product is substantially nil, generally running about 1 to 2 at the most.

An examination of such reactions is best conducted on a laboratory scale. In other words, if one were to start with approximately 650 grams of the mixture described under the heading Triricinolein fractional ester, Example 1, and having an acid value of approximately 105, and add thereto the equivalent of 2 /2 moles of a polyethyleneglycol having approximately 10 to 11 Such reaction can be conducted in any one of three ways: (a) Absence of a catalyst; (b) presence of an acid catalyst, or (0) presence of a basic catalyst. Actually, there is little or no justification for using a basic catalyst, for the reason that under such circumstances, one would not expect to obtain a product comparable to that described under the heading Water-soluble oxyethylated triricinolein fractional ester, but would expect to get a product to which a large degree of glycerol had been replaced by the nonaethylene glycol with subsequent corresponding reaction. In other words, one would expect transesterification, which is sometimes referred to as ester-interchange or alcoholysis. (See Organic Chemistry, Fieser and Fieser, page 182, D. C. Heath and Company, Boston, 1944, and Organic Chemistry, Fuson and Snyder, page 92, J. Wiley 8; Sons, New York, 1942.)

In conducting these exploratory experiments, it becomes obvious that the two end points do not coincide, namely, the elimination of the expected amount of water and reduction of the acidity to the value of 1 or 2. In each instance, an attempt was made to carry the reaction to the end point indicated in both ways. In the case of the acid catalyst, /g% of p-toluene sulfonic acid was added. In connection with the polyethylene glyco1 reactant, attention is directed to the article entitled Technology of the polyethylene glycols, and Carbowax compounds," Chemical and Engineering News, volume 23, No. 3, page 247 (1945). Such article points out, among other things, why the value of n as herein contemplated represents an average value rather than a sole value of one single compound. The results of these experiments are indicated in the following table:

Triricinoleln Fractional Ester Example 1 (011140) nH(7L=10 or 11)v catalyst Acid value of Mixture. Conditions to bring acid value to about 2 Time Max. Temperatu e At this point Hi0 eliminated.

Remarks Conditions to'bring about elimination of 17% Acid value at this point.

Remarks Clear oil; cloudy solu tion with water.

Acid v. rose upon further heating.

tion with water.

Acid Value rose upon further heating.

20.4. Clear oil; cloudy solu tion with water.

In comparison with experiments- 33;..and C, it has been pointedout'previously; as in Watersoluble ox-yethy'lated triricinolein" fractional ester," that such reactant as-wasused in experiments A, B; and-:6, cambe -treated with ethylene oxide under a comparatively low temperature, approximately 120" C5, iii-absence of water, to give a::-productwhich is clearly water soluble.- and which has-an average an olecular weight approx:- imatelywequivalent. tothat of: the prod-ucts ob tained; in experiments A, B, andrC, provided --that there was completechemical combination. 'I-he acid value of. the. oxyethylatedederivative:wasapproximatelyfl: -In examining experiments A, B; and"C,. it is to he? noted that it was: impossible to. reduce the acid valuein. any one, of. the three-cases to -that obtainable byoxyethylation, to wit, a valueiof 2. Actually, the valuese'rangefrom-approximately 8 to '14. Furthermore, thetheoretical amount of water which would be expected. to be eliminated inrexperiments A, B, and C, so'asto givea-productiidentical withthat. previously referred to as Example-1:, .would be 17 .-grams of water. Actually-,- when 171/2 "gramsof water had been elimie nated. i-n-uall; three cases, the acidvalue varied from approximately-20 1 to fapproxim ately 33. On the-other hand,,w-hen the-minimum acid value was-obtained, eventhough it did. not approach the, value of: two-the amountof Water eliminated was .a-rgreat deal. more than theoretical. varying from 5&- grams in-c-nednstancer, to 346 grams in the other:. Furthermera, in order to "obtain: the result'.'indicated,.instead of using atemperature of? approximately- 130. C. or somewhat higher, but in any event under 200. C..,,the temperature actually varied-from 230 C. to: 340 C. Attention is directed to. a very significant fact and that-is that these temperatures employedin ex.- periments A, B,.and.C., as previously noted, vary fronr230 C. to'340 0., and-are within the range which produces rearrangement in thezman-ufacr tureof acidic esters aspreviously noted. Inother words, at suchtemperature range, even though no-catalystswere added, one wouldexpect-rear rangementswherebyat least. to a substantial exatent; thererwould be present. compounds inewhich the dicarbexy-acld radical wouldbe-directly at!- tached to theiglyceryrradical. It is.-.to be= noted thattthis: type of material-is" specifically. excluded inthe-hereto appended claims.

IEn-light of what hasbeen said'as tothe nature ai -the: reactions taking place, and as to' theresults; obtained in the above experiments, itis perfectly-obvious that there is a very markeddifference the nature. of theproducts: obtained, depending on whether an acidic fractional ester is subjected to oxyethylation' or whether it: is subjected to-an esterification with a polyglycolin mneffort'tto' obtain substantially the same prod uct;. although: for sake of brevity, reference is made. only to products obtained by phthalation, actually other experiments conducted with other polycarboxy acids, particularly succinic' acid, adipic-acid, diglycolic acid, etc, indicate-that re"- -s'ults:.ar.e substantially the same.

Inlight of the experiments above-(recited; it is obvious thatiiffione takes a product such as triricinolein monophthalate; triricinolein diiphthalate; triricinolein triphthalate, or' an"; analogous fractional ester derived from some other polycarhoxy acid such asadipic acid, suc- -cinic=acid, maleic acid, or adductacids of-succinicor-maleic acids, or the'like; one canolitain variety I of products which are characterized by the' fa'ct'that they are dehydrated inr-theesensethat the amountof water-eliminated during-the reaction is approximately twice theoretical re;-

cuired to eliminate theiree carboxyl radicals;

and the products are also: characterized addittionaily by the fact that there is st'ill a significant residual acidity; Conditions seem tozbe approxie mately the same regardless 'of whetherawcatalyst is used or. no catalystis used. The catalyst may be an acid, such as an aromatic:sulfonicwacid; or it maybe an alkalinemater-ial such. as sodium stearate, sodium carbonate, caustic soda, sodium methylate, etc; Inorder to illustrate-this:v type of reaction, the following.- illustrations are inciuded which, for convenienc'eare substantiallythe large" scale equivalents of experiments: A, B and C.

FINAL COMPOSITION OF Example 1 650 pounds of amaterial of the kinddescrihed under the heading. Triricinolein acidic fractional ester, Example 1, is mixed with approximately 'lGO pounds ofa polyethylene glycol consistingpof a of'nonaethylene glycol, decaethylene glycol, and undecaethylene glycol, orif. desired one'may use approximately 10% less of: nonaethylene glycol, that is, about 630 pounds. of nonaethylene glycol. The products are. heated without a catalyst for approximately. 3.v hours with constant stirring, at about 320 C. to 350 C. At the end of this time, the-amount" of water eliminated is approximately, pounds or slightly more. In addition to this amount of water, which leaves the reaction vessel,,there-: is: also somewhere-in-encessvoi: 50 pounds. of oil. eliminated.

It'is to benoted in this respect that the themretical'; amount of: water; approximately 157 /1 pounds, is eliminated at a pointrblelow; thea pyrclytic' point oifitriricinoleinrthat is it is 611ml.- nated: bythe time 275 to 280C; is reached, particularly. if heidatthis temperature for about 40 minutes. Theappearanceof oil andzthe fact that the temperaturewis above: the pyrolyticz point of triricinolein; is; a" strong: indication-that; oer:- taincom-plex changestalie place, such as" appear in the: dehydration: of castor oil; The nature. of these changes is rather; difficult to determine. For convenience, reference is madeto Protective and Decorative-Coatings byz'Mattiellc; volume I, chapter 4,- John Wiley trsons; Inc, New-York 1941); However, the-fact that dehydratiorr of the triricinolein has" taken place (phthalic acid being split oii instead: of water. but: the reaction being: the same; for example; aszwhen castono'il ispfirst' acetylated andrthensubjccted to dehydratgivinga cloudy solution in water; llhe acid value of: the-final productiafter being-heated to amax:- imumoft 2410. C: isiapproximately 15;.

FINAL COMPOSITION: OFJVIATTER5 Example; 22

The preceding example is repeatedj but there is added to the reaction 1 mass: 2i. catalystzccnsisting of approximately.7%..nounds of toluene sulfonic acid. complete reactioncouid' be obtained eta Iewer In this instance it was found that temperature than when no catalyst was employed, for instance, at a maximum of 300 0., provided the reaction was continued somewhat longer, for instance, about 4 to 6 hours instead of 3 hours; Also, in the use of the acid catalyst, the amount of water eliminated was unusually large, approximately five times that eliminated in the previous example, to wit, 345 pounds. Note that in the example previously shown and in the present instance, water refers to the aqueous distillate which may contain other water-soluble materials. The final product was comparable in all respects to the product obtained without use of a catalyst. The fact that the catalyst speeded up the reaction is also indicated by the fact that the theoretical amount of water, 17 pounds, could be eliminated in 25 minutes at 230 C. At this point, i. e., at the point where the theoretical amount of water was eliminated, the product was more acidic than the comparable product made without a catalyst, for instance, showing an acid value of about 34. It is to be noted that the amount of water eliminated under these circumstances is unusually high and difficult to explain on any rational basis. The destruction of the polyglycol radical is not indicated by the fact that the final product is still as hydrophile as if no catalyst were used or as if an alkaline catalyst were used. The amount of water eliminated simply points to the complexity of the reaction but offers no satisfactory explanation.

FINAL COMPOSITION OF MATTER Example 3 The same procedure was used as previously, except that the catalyst employed was approximately 7 pounds of sodium methylate. The reaction was heated for approximately 4 hours at 325 C. with the elimination of 55 pounds of water and 15 pounds of a water-insoluble oil. The acid value was reduced to a maximum of about 8, but increased somewhat subsequently. The theoretical amount of water, to wit, 17 pounds, was eliminated in three-quarter hours of heating at 285 C. The acid value at this point dropped to less than one-half the original value or about 20. The final product was comparable to the materials obtained in the two previous examples.

Due to the fact that the castor oil dehydrates *and probably forms, at least in part, conjugatedbonds which lead to a Diels-Alder adduct, or in view of the fact that a Clocker type adduct could be formed at such temperature, we have specified that the polycarboxy acids of the type having unsaturated bonds, such as maleic acid or anhydride, and citraconic acid or anhydride, should 'be avoided. We have found that this type of polycarboxy acids is much less satisfactory and, in fact, very apt to yield rubbery or almost insoluble masses. For this specific reason it is our preference to use polycarboxy acids, such as phthalic acid or anhydride, adipic acid, diglycolic acid, etc., i. e., materials which cannot form olefinic addition products by virtue of the reactive ethylenic structure. This, of course, does not interfere with the use of products obtained by first reacting maleic anhydride, citraconic anhydride or the like, with butadiene, cyclopentadiene, or other suitable reactants capable of addition.

.FINAL COMPOSITION OF MATTER v I Example 4 The same procedure is followed as in Examples 16 1 to 3, preceding, except that the fractional ester exemplified by Triricinolein acidic fractional ester, Example 1 is replaced by Triricinolein acidic fractional ester, Example 3.

FINAL COMPOSITION OF MATTER Example 5 The same procedure is followed as in Examples 1 to 3, preceding, except that the fractional ester exemplified by Triricinolein acidic Fractional ester, Example 1, is replaced by Triricinolein acidic fractional ester, Example 4.

In connection with these reactions, it will be noted that as previously pointed out, the reactions are conducted at a temperature above the pyrolytic point of triricinolein (castor oil), which is commonly accepted as being about 265 to 280 C. but, in any event, the reaction is not conducted at a temperature higher than 365 C. and preferably within the range of 300 C. to 340 C. The reaction may be conducted in the presence or absence of a catalyst and preferably is conducted in the presence of an alkaline catalyst. In each cas the reaction is conducted so that the amount of water eliminated is at least twice theoretical as would be obtained by reaction of the carboxyl radicals alone and, in any event, the final product still has a significant acid value. The products obtained must be capable of giving at least cloudy solutions or sols with water and thus are character stically hydrophile. The expression hydrophile is used to distinguish from such products which may become sub-resinous or sub-rubbery so as to no longer exhibit hydrophile properties, at least they are not even selfemulsifying in water.

In light of what has been said, it is obvious that the only way these materials can be characterized, is by the method of manufacture. Since the method of manufacture involves the reduction in both the carboxy value and hydroxyl value of the mixture reactants, it is obviously esterification. Since it involves the elimination of water over and above that which is represented by the esterfication reaction per se, one must include pyrolysis. Thus, for convenience, we are referring to this reaction in what appears to be the most suitable terminology-as a pyrolytic esterification reaction. The mixture reactants should be such that the amount of glycol added is at least, stoichiometrically, equivalent to one carboxyl radical of the acidic fractional ester and preferably is, stoichiometrically, equivalent (based on elimination of one hydroxyl only by the poly-glycol) to all the carboxyl radicals present in the acidic fractional ester. It has been previously indicated why polycarboxy acids, partic' ularly dicarboxy acids having alpha-beta unsaturations, are excluded, namely, for the reason that such dienophylic acids may enter into complex reactions giving resinous or rubbery resultants which are unsatisfactory and exhibit little or no hydrophile properties.

Conventional demulsifying agents employed in the treatment of oil field emulsions, are used as such, or after dilution with any suitable sol-3 vent, such as Water; petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol etc. may be employed as diluents. Miscellaneous-solvents such as pine oil, carbon tetrachloride, and sulfur dioxide, extract obtained in the refining of aasoaesai ipetroleuin, feta, may be employed as 'I'diluents. similarly, theimateria l or materials employed'as z-the 'tdemulsifying agent of our r process, may be admixed with one or more 'oi'the solvents'customarily used rin 'connection:with conventional demulsifying agents. --materialsmay beuse'dialona'or in admixture with other suitable well-"known-classes f demulsifying Moreover,-said material or agents.

It is well known that conventional demulsifyeven 1 to"40,000 or Ito- 50,000 "in desaltingprac- -tice, such anapparent insolubility in ciland water is notsigniiicant because said reagents undoubtedly have solubility within the concentration-employed. Thissame'fact'is true in regard tothe material or :materials employed as the demulsifying agent of our process.

We desire to point out that the superiority of the reagent or demulsiry'ing agent contemplated in our process, is based-upon its ability to treat certain emulsions In'oreadvantageou'sly and at somewhat lower cost than-"ispossible with other available demulsifiers, or conventional mixtures thereof. Itis believe'd thattheparticular demulsifying' 'agent'or treating agent herein described, will find comparatively limited appli- *cation so 'iar -as the 'majority ofoil .field emulsions are concerned, but -we have found that such a demulsiiying agent has commercial value as it will economically breaker resolve oil field "emulsions 'in a-num-ber (bf-cases which cannot be treated as easily or at so slow a cost'with the demulsifying agents'here'tofore available.

In practicing our processior resolvingpetro- 'leur'n emulsions =of the water-in-oil' type. a treating agent or demulsi-fying agent of thekind above described, is brought into contact with or caused demulsifying procedure, such as the electrical dehydration process.

The demulsifier'herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. .e., bringing the demulsifierin contact with the fluids of the well at the bottom 'ofthe' well, or .at some point priorltothe emergence of said fluids. particular type of applica'tionis decidedly feasible whenthe dernulsifi'er is used'in connection with acidification of calcareous oil-bearing strata, -es peciallyir" suspendedin .or'dissolved in the acid employed for acidification.

A somewhat analogous use of our demolsifying agent is in the removal of a residual mud sheath which remains after drilling a well by the rotary method. See U. S. Patent No. 2,135,909, dated November 8, 1938, to 1 10118011. Sometimes the drilling mud contains added calcium carbonate 0 the -ke to render the mud susceptible to reaction with hydrochioric acid or the like, and thus expedite its removal. Our compound is particularly adapted for use in connection with such treatment involving the use of strong mineral acid.

One preferred and more narrow aspect of our invention "insofar as it is concerned with demulsi- *fication of petroleum'z-emulsions of the water-inoil type, is concernedwith the admixture ofthe ester as described, with -a'viscosity reducing solvent such as' the various 'solvents'enumerated, particularly aromaticsolvents, alcohols, ether alcohols, etc, as 'previous'ly specified. "The word. solvent is usedinthis sense to refer tothe mixture if more than one solvent is employed, and generally speaking .it is our preference to employ the demulsifier in a .form representing40% to 85 demulsifier and '15 "to solvent; largely, if'not entirelynonaqueous and so selectedas to give a solution or'mixture particularly adaptable for'proportional pumps or other measuringtdevices, Theiollowing. examples will illustratetthis aspect of ourinvention.

mama

Example -1 Percent -E'ster, exemplified b Final composition of --matter;Example-1. 60 -Xylene 20 Isopropyl'alcohol r20 "DEMULSIFIER Ewample '2 Percent Ester, exemplified by Final composition "of matter, Example 2; L70 Cresylic acid 20 Normal butyl alcohol. '10

*DEM'ULSIFIER Example 3 "Per cent Ester, exemplified by Final composition of matter, Example 3 70 Aromatic petroleum solvent 10 Isobutyl alcohol 10 Acetone 10 DEMULSIFIER Example 4 Per cent Ester, exemplified by Final composition of n1atter,'EXample-4 '(esterobtained by use of alkaline'catalyst) Methyl alcohol 15 Dichloroethylether 20 (The above proportions represent percentage by weight.)

In'the hereto appended claims'the word Watermiscible is employed to designate a 501 or solution which is permanent for either an indefinite period oftime or either'forsuch 'extended'period oftime as would unquestionably permitits utilization fo-r'the herein designated purposes without'un'due difficulties.

For reasons previously stated, the product herein contemplated, and particularly for use as a demulsifying agent, is conveniently described as a hydrophile pyrolytic esterification product derived by reaction between (A) an acidic triricinolein ester of a dicarboxy acid having not over 16 carbon atoms and characterized by the fact that there is present at least one dicarboxy acid carboxyl radical for each triricinolein radical, and all dicarboxy acid radicals are directly attached to the ricinoleyl radicals; and (B) a polyalkylene glycol having at least 8 and not more than 1'7 ether linkages and the alkylene radical thereof containing at least two and not more than In our co-pending application Serial No.

666,819, filed May 2, 1946, we have included a series of comparative tests showing the much greater effectiveness of the compounds therein contemplated on a number of typical emulsions, compared with the compounds herein contemplated. It has been our experience that on an equivalent basis such compounds as contemplated in the aforementioned co-pending application Serial No. 666,819 are usually better and more effective. However, we have also found a sizable number of emulsions wherein the compounds herein contemplated appear to be better than any other compound available. They seem to be made-to-order, so to speak, for such specific emulsions. Also, We have found instances in break inducing in the doctor treatment of sour hydrocarbons, where these particular reagents are more efiective than are others available. In other words, even though we recognize that compared with many other types, those herein contemplated may have rather limited utility, yet there are instances where they seem to serve more effectively and more economically than any others with which we are now acquainted.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent, is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a hydrophile pyrolytic esterification product derived by reaction between (A) an acidic triricinolein ester of a dicarboxy acid having not over 10 carbon atoms and characterized by the fact that there is present at least one dicarboxy acid carboxyl radical for each triricinolein radical, and all dicarboxy acid radicals are directly attached to the ricinoleyl radical, and (B) a polyalkylene glycol having at least 8 and not more than 17 ether linkages and the alkylene radical thereof containing at least 2 and not more than 6 carbon atoms; said pyrolytic esterification product being further characterized by the fact that it is the resultant of a pyrolytic esterification reaction conducted within the temperature range of 265 C. to 3 5 C., with the proviso that (a) the amount of water evolved during said pyrolytic esterification is at least twice that theoretically obtainable from the 20 complete reaction of the free carboxyl radicals present, and that (b) said resultant of the pyrolytic esterification reaction still has a significant acid value.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a hydrophile pyrolytic esterification product derived by reaction between (A) an acidic triricinolein ester of a dicarboxy acid having not over 10 carbon atoms and characterized by the fact that there is present a plurality of dicarboxy acid carboxyl radicals for each triricinolein radical, and all dicarboxy acid radicals are directly attached to the ricinoleyl radical; and (B) a polyalkylene glycol having at least 8 and'not more than 17 ether linkages and the .alkylene radical thereof containing at least 2 and not more than 6 carbon atoms; said pyrolytic esterification product being further characterized by the fact that it is the resultant of a pyrolytic esterification reaction conducted within the temperature range of 265 C. to 365 C., with the proviso that (a) the amount of water evolved during said pyrolytic esterification is at least twice that theoretically obtainable from the complete reaction of the free carboxyl radicals present and that (b) said resultant of the pyrolytic esterification reaction still has a significant acid value.

3. The process of claim 2 wherein the polyethylene glycol radical is a nonaethylene glycol radical.

4. The process of claim 2 wherein the polyethylene glycol radical is a nonaethylene glycol radical, and the dicarboxy acid radical is a phthalic acid radical.

5. The process of claim 2 wherein the polyethylene glycol radical is a nonaethylene glycol radical, and the dicarboxy acid radical is an adipic acid radical.

6. The process of claim 2 wherein the polyethylene glycol radical is a nonaethylene glycol radical, and the dicarboxy acid radical is a diglycolic acid radical.

MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,977,146 Roberts Oct. 16, 1934 1,978,227 Roberts Oct. 23, 1934 2,000,717 Roberts May 7, 1935 2,023,995 De Groote et al. Dec. 10, 1935 2,236,516 Cahn et a1. Apr. 1, 1941 2,340,355 Wirtel Feb. 1, 1944 2,401,966 Salathiel June 11, 1946 2,423,364 Blair et al July 1, 1947 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TOT HE ACTION OF A DEMULSIFYING AGENT COMPRISING A HYDROPHILE PYROLYTIC ESTERIFICATION PRODUCT DERIVED BY REACTION BETWEEN (A) AN ACIDIC TRIRICINOLEIN ESTER OF A DICARBOXY ACID HAVING NOT OVER 10 CARBON ATOMS AND CHARACTERIZED BY THE FACT THAT THERE IS PRESENT AT LEAST ONE DICARBOXY ACID CARBOXYL RADICAL FOR EACH TRIRICINOLEIN RADICAL, AND ALL DICARBOXY ACID RADICALS ARE DIRECTLY ATTACHED TOT HE RICINOLEYL RADICAL, AND (B) A POLYALKYLENE GLYCOL HAVING AT LEAST 8 AND NOT MORE THAN 17 ETHER LINKAGES AND THE ALKYLENE RADICAL THEREOF CONTAINING AT LEAST 2 AND NOT MORE THAN 6 CARBON ATOMS; SAID PYROLYTIC ESTERIFICATION PRODUCT BEING FURTHER CHARACTERIZED BY THE FACT THAT IT IS THE RESULTANT OF A PYROLYTIC ESTERIFICATION REACTON CONDUCTED WITHIN THE TEMPERATURE RANGE OF 265*C. TO 365*C., WITH THE PROVISO THAT (A) THE AMOUNT OF WATER EVOLVED DURING SAID PYROLYTIC ESTERIFICATION IS AT LEAST TWICE THAT THEORETICALLY OBTAINABLE FROM THE COMPLETE REACTION OF THE FREE CARBOXYL RADICALS PRESENT, AND THAT (B) SAID RESULTANT OF THE PYROLYTIC ESTERIFICATION REACTION STILL HAS A SIGNIFICANT ACID VALUE. 